Internal combustion engine exhaust gas purification apparatus, exhaust gas purification process and exhaust gas purification catalyst

ABSTRACT

Nitrogen oxides contained in an exhaust gas emitted from a lean-burn engine-mounted internal combustion engines are eliminated with a high efficiency.  
     In an exhaust gas purification apparatus and process for eliminating nitrogen oxides contained in a combustion exhaust gas emitted from an internal combustion engine with a reducing gas such as carbon monoxide, hydrocarbons, etc. contained in the exhaust gas in the presence of a catalyst, a catalyst comprising all of Rh, Pt and Pd, at least one member selected from alkali metals and alkaline earth metals, and Mn or its compound, supported on a porous carrier is used.

TECHNICAL FIELD

[0001] The present invention relates to an exhausts gas purification apparatus, an exhaust gas purification process and an exhaust gas purification catalyst with high elimination efficiency of NOx from NOx-containing exhaust gases such as combustion exhaust gases from internal combustion engines such as automobile engines, etc.

BACKGROUND ART

[0002] Lean-burn engines capable of bringing an air/fuel ratio into a fuel-lean stage have been nowadays regarded as promising automobile internal combustion engines from the viewpoint of reduced fuel consumption. However, the exhaust gases from such engines are in such an oxidizing atmosphere that the O₂ concentration of the exhaust gases is more than a stoichiometric amount necessary for complete combustion of reducing components contained in the exhaust gases (said atmosphere will be hereinafter referred as “oxidizing atmosphere”). The conventional ternary catalysts are directed to efficient purification of NOx, HC and CO in such a reducing atmosphere that the O₂ concentration of the exhaust gases is not more than a stoichiometric amount necessary for complete combustion of reducing components contained in the exhaust gases (said atmosphere will be hereinafter referred to as “reducing atmosphere”), failing to show a satisfactory NOx elimination activity in the oxidizing atmosphere. Thus, it has been keenly desired to develop catalysts capable of effectively eliminating NOx, HC and CO, particularly NOx, in the oxidizing atmosphere.

[0003] For exhaust gas purification directed to the lean-burn engines, WO93/07363 and WO93/08383 propose to provide an NOx absorbent in the exhaust gas passage. The NOx absorbent can absorb NOx from the exhaust gases during the fuel-lean combustion and discharge the absorbed Nox when the O₂ concentration of the exhaust gases is lowered.

[0004] JP-A-8-299793 also proposes to provide a catalyst which comprises an NOx-absorbing component capable of absorbing NOx from the exhaust gases during the fuel-lean combustion and an NOx-reducing component capable of reducing the absorbed NOx in the exhaust gas passage.

[0005] With more and more intensified atmospheric regulation of the automobile exhaust gases, much higher NOx elimination activity and durability are required for the Nox elimination catalysts directed to the lean-burn engines. The present invention provides an exhaust gas purification catalyst with distinguished NOx elimination activity and durability, particularly distinguished head resistance and SOx resistance, an exhaust gas purification apparatus and an exhaust gas purification process using said catalyst.

DISCLOSURE OF THE INVENTION

[0006] The present invention is directed to elimination of NOx in a combustion exhaust gas in an oxidizing atmosphere emitted from an internal combustion engine with a catalyst comprising a carrier and active components, the active components comprising at least one of Rh, Pt and Pd, at least one member selected from alkali metals and alkaline earth metals, and Mn.

[0007] One member selected from the alkali metals and alkaline earth metals can serve the desired purpose, but two or more members thereof can further improve the activity. It seems that new active sites are formed on the catalyst owing to two or more members of these metals supported on the carrier. An amount of supported alkali metals and alkaline earth metals is preferably in a range of 0.05 to 3 parts by mole each of the supported metals in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier, where “parts by mole” means a proportion of one component to another in terms of moles; for example, “3 parts by mole of supported component B to 1.5 parts by mole of component A” means that component B is supported in a ratio of component B to component A being 3:1.5 terms of moles, irrespective of the absolute amount of component A. In case the amount of supported alkali metals and alkaline earth metals is less than 0.05 parts by mole each, the improvement of NOx elimination activity is less effective, whereas in case of more than 3 parts by mole the specific surface area of the alkali metals and alkaline earth metals becomes undesirably smaller.

[0008] The porous carrier may be supported on a substrate, where 0.3 to 4 moles of the porous carrier can supported on 1 l of the substrate preferably from the viewpoint of NOx elimination activity. In case the amount of supported porous carrier is less than 0.3 moles, the dispersibility of active components becomes poor, whereas in case of more than 4 moles the specific surface area of the porous carrier itself becomes undesirably smaller.

[0009] Mn is present in the form of metal or an oxide or a composite oxide with Al, etc. and seems to serve to capture NOx in the oxidizing atmosphere and further serve to improve the high temperature durability of the catalyst. By inclusion of both of at least one member of the alkali metals and alkaline earth metals and Mn the NOx-capturing effect can be further improved.

[0010] An amount of supported Mn is preferably in a range of 0.05 to 2 parts by mole in terms of metal element on the basis of 1.5 parts by mole of the porous carrier. In case the amount of supported Mn is less than 0.05 parts by mole, the effect is not remarkable, whereas in case of more tan 2 parts by mole the specific surface area of the catalyst becomes undesirably smaller.

[0011] Rh, Pt and Pd can enhance the elimination activity and high temperature durability. It is most desirable for the improvement of the activity and durability to contain all of these noble metals.

[0012] Amounts of supported noble metals are preferably in ranges of 0.002 to 0.05 parts by mole of Pt, 0.0003 to 0.01 part by mole of Rh and 0.001 to 0.2 parts by mole of Pd, all in terms of metal elements, on the basis of 1.5 parts by mole of the porous carrier. In case the amount of supported noble metals are less than their lower limits the effect is not remarkable, whereas in case of more than the upper limits the specific surface areas of the noble metals per se become smaller without remarkable effect.

[0013] When at least one of rare earth metals is supported thereon in addition to the foregoing components, the NOx elimination activity and high temperature durability can be further improved, where it is preferable to contain 0.02 to 0.5 parts by mole of each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier. In case of less than 0.02 parts by mole, the effect is not remarkable, whereas in case of more than 0.5 parts by mole the specific surface area of the catalyst becomes undesirably smaller. Preferable rare earth metals are La, Nd and Ce.

[0014] By further adding at least one of Ti and Si thereto, the NOx elimination efficiency and also the SOx resistance can be further improved. It seems that the effect of Ti and Si on the SOx resistance improvement is due to Ti and Si being formed into composite metals together with Mn, alkali metals and alkaline earth metals. By further adding at least one of Co, Ni and Cu thereto, the NOx elimination activity and the heat resistance can be further improved. Amounts of supported Ti, Co, Si, Ni and Cu are preferably in a range of 0.01 to 2 parts by mole of each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.

[0015] The present catalyst can further contain at least one of B and P.

[0016] B and P are present in the form of simple substances or oxides or composite oxides with at least one member selected from alkali metals and Al, and seem to serve to capture NOx in the oxidizing atmosphere, play a role of attracting CO, hydrocarbons, etc. as reducing agents onto the catalyst surface and serve to further improve the heat resistance and the SOx resistance of the catalyst. By controlling mixing sequence of B or P or firing temperature, etc. during the catalyst preparation, they can be brought into the oxide form or the composite oxide form.

[0017] An amount of supported B or P is preferably in a range of 0.01 to 2 parts by mole of each in terms of elements on the basis of 1.5 parts by mole of the porous carrier. In case of less than 0.01 part by mole of supported B or P the effect is not remarkable, whereas in case of more than 2 parts by mole the specific surface area of the catalyst becomes undesirably smaller.

[0018] The catalyst can be prepared by any procedure utilizing physical means or chemical reactions such as impregnation, kneading, coprecipitation, sol-gel formation, ion exchange, vapor deposition, etc.

[0019] Starting materials for use in the catalyst preparation include various compounds such as nitrate compounds, acetate compounds, complex compounds, hydroxides, carbonate compounds, organic compounds etc., metals and metal oxides.

[0020] For the porous carrier, metal oxides, composite oxides, etc. such as alumina, titania, silica, silica-alumina, zirconia, magnesia, etc. can be used, among which alumina is most preferable. The present catalyst can be used upon coating onto a substrate. Cordierite is a most suitable substrate, but even a metal such as stainless steel can be used as well.

[0021] The NOx elimination catalyst can be used in any form, for example, honeycomb form, pellet form, plate form, granule form, powder form, etc., among which the honeycomb form is most preferable.

[0022] The present catalyst has an effect of eliminating NOx contained in the exhaust gases emitted from internal combustion engines during the lean-burn operation with high elimination efficiency. The NOx elimination effect of the present catalyst seems due to an action of capturing NOx contained in the lean-burn exhaust gas on the catalyst surface, thereby eliminating NOx from the exhaust gas and an action of reducing the captured NOx, thereby eliminating it. Capturing of NOx seems to be effected by absorption, chemisorption, etc.

[0023] The exhaust gas during the lean-burn operation contain oxygen at a higher concentration than the stoichiometric amount necessary for complete combustion of reducing components (HC and CO) in the exhaust gas and thus is in an oxidizing atmosphere. The exhaust gas in an oxidizing atmosphere will be hereinafter referred to as “lean exhaust gas” or “air/fuel ratio-lean exhaust gas”. An exhaust gas emitted from internal combustion engines upon combustion in a theoretical air/fuel ratio will be hereinafter referred to as “stoichiometric exhaust gas” or “air/fuel ratio-stoichiometric exhaust gas”. An exhaust gas emitted from internal combustion engines operated in fuel excess over the theoretical air/fuel ratio contains oxygen at a lower concentration than the stoichiometric amount necessary for complete combustion of the reducing components contained in the exhaust gas and thus is in a reducing atmosphere. The exhaust gas in a reducing atmosphere will be hereinafter referred to as “rich exhaust gas” or “air/fuel ratio-rich exhaust gas”.

[0024] One embodiment of the present invention provides an exhaust gas purification apparatus provided with said catalyst in the exhaust gas passage from internal combustion engines in lean-burn operation.

[0025] Another embodiment of the present invention provides an exhaust gas purification process for purifying an exhaust gas emitted by lean-burn operation upon contacting the exhaust gas with said catalyst.

[0026] When the present catalyst is kept in continuous contact with an air/fuel ratio-lean exhaust gas, the NOx elimination efficiency will be gradually lowered, because the amount of captured NOx on the catalyst surface gradually increases, thereby weakening the capturing action. When the NOx elimination efficiency is so lowered, it is desirable to temporarily shift the lean-burn operation to a theoretical air/fuel ratio operation or a fuel excess operation, thereby bringing the air/fuel ratio of the exhaust gas into a stoichiometric or fuel-rich exhaust gas, the NOx elimination action can proceed so actively that the NOx captured on the catalyst surface can be rapidly eliminated to regenerate the catalyst. Thus, when the operation is shifted again to the lean-burn operation once again, high NOx elimination efficiency can be obtained. The duration of the theoretical air/fuel ratio or fuel excess operation is only a few seconds to a few minutes.

[0027] The present catalyst can be used in combination with a combustion catalyst capable of combusting HC and CO. For the combustion catalyst capable of combusting HC and CO, it is desirable to use a catalyst comprising Pt and Rh supported on an alumina carrier or a catalyst comprising Ag and Mn supported on an alumina carrier. The combustion catalyst can be provided at a position upstream or downstream of the present catalyst or at both upstream and downstream positions.

BRIEF DESCRIPTION OF DRAWINGS

[0028]FIG. 1 is a schematic view of an exhaust gas purification apparatus according to one embodiment of the present invention.

[0029]FIG. 2 is a view showing an NOx elimination catalyst and a combustion catalyst provided in an exhaust gas passage from an automobile engine.

BEST MODES FOR CARRYING OUT THE INVENTION

[0030]FIG. 1 shows one embodiment of the present exhaust gas purification apparatus.

[0031] In FIG. 1 are shown a lean-burn engine 99, a suction system comprising an air cleaner 1, an air flow sensor 2 and a throttle valve 3, an exhaust gas purification system comprising an oxygen concentration sensor 7, an exhaust gas temperature sensor 8, a catalyst outlet gas temperature sensor 9, an exhaust gas purification catalyst 10, etc., an engine control unit (ECU) 11, etc. ECU 11 comprises an I/O as an input/output interface, an LSI, a microprocessing unit (MPU), memory units RAM and ROM memorizing a large number of control programs, a timer/counter, etc.

[0032] Suction air to the engine is filtered through the air cleaner, then metered by the air flow sensor 2, passed through the throttle valve 3, subjected to fuel injection from an injector 5, and fed to the engine 99 as a mixed gas. Air flow sensor signals and other sensor signals are input into the ECU (Engine Control Unit) 11.

[0033] ECU evaluates the operating state of the internal combustion engine and the state of the exhaust gas purification catalyst and judges an operating air/fuel ratio, thereby controlling the injection time of the injector 5, etc. to set the fuel concentration of the mixed gas to a desired value. The mixed gas introduced into the cylinder is ignited by an ignition plug 6 controlled by a signal from ECU 11 and combusted. The combustion exhaust gas is led to the exhaust gas purification system. The exhaust gas purification system is provided by the exhaust gas purification catalyst 10, which eliminates NOx, HC and CO in the exhaust gas by its ternary catalyst function during the stoichiometric operation, and eliminates NOx by the NOx capturing function and also eliminates HC and CO by the combustion function at the same time during the lean operation. The NOx elimination activity of the exhaust gas purification catalyst is always determined during the lean operation by the judgement of EUC and control signals to shift the air/fuel ratio, etc. to the fuel-rich state during the combustion, when the NOx elimination activity is lowered, thereby regaining the NOx capturing action of the catalyst. By the foregoing operations, the exhaust gas can be effectively purified under all the engine combustion conditions of lean operation and stoichiometric operation (including the fuel-rich operation). An A/F sensor can be used in place of the oxygen concentration sensor 7.

[0034]FIG. 2 shows the case of providing a hydrocarbon and CO combustion catalyst downstream of the exhaust gas purification catalyst 10. In FIG. 2, the remaining hydrocarbon and CO as not eliminated by the exhaust gas purification catalyst are eliminated by the combustion catalyst 20.

[0035] The present invention will be described in detail below, referring to Examples, which are not limitative of the present invention.

EXAMPLE 1

[0036] A cordierite honeycomb (400 cells/inc²) was coated with a slurry prepared from alumina powder and alumina precursor and made acidic by nitric acid, dried and fired to obtain an alumina coat honeycomb as coated with 1.5 moles of alumina per 1 l of the apparent honeycomb volume. The alumina coat honeycomb was impregnated with a mixed solution of dinitrodiamine Pt nitric acid solution and Rh nitrate solution, dried at 200° C. and then fired at 600° C. Then, the supported Pt and Rh-contained honeycomb was impregnated with a mixed solution of Na nitrate solution, Mn nitrate solution and Pd nitrate solution, dried at 200° C. and then fired at 600° C. Thus, Example catalyst 1 containing 0.0022 parts by mole of Rh, 0.014 parts by mole of Pt, 0.8 parts by mole of Na, 0.2 parts by mole of Mn and 0.014 parts by mole of Pd in terms of metal elements on the basis of 1.5 parts by mole of alumina was prepared. The catalyst will be hereinafter expressed as 0.8 NaMnPd—RhPt/Al₂O₃. Likewise, Example Catalysts 2 to 9, which contained 0.8 parts by mole each of Li, K, Rb, Cs, Mg, Ca, Sr and Ba, respectively, as supported in place of Na, while changing the amounts of supported Mn, Pd, Rh and Pt, and Example Catalysts 10 to 41 containing at least two members of alkali metals and alkaline earth metals without changing the amounts of supported Mn, Pd, Rh and Pt were prepared. In the same manner as for Example Catalyst 1, Comparative Example Catalysts 1 to 9 containing 0.0022 parts by mole of Rh, 0.014 parts by mole of Pt, 0.014 parts by mole of Pd and 0.8 parts by mole of each of Na, Li, K, Rb, Cs, Mg, Ca, Sr and Ba in terms of metal elements respectively, as supported on the basis of 1.5 parts by mole of alumina, without containing Mn, and likewise Comparative Example Catalysts 10 to 14 containing at least two members of alkali metals and alkaline earth metals without containing Mn and without changing the amounts of supported Pd, Rh and Pt, were prepared as Comparative Example Catalysts.

TEST EXAMPLE 1

[0037] (Test Procedure)

[0038] The foregoing catalysts were subjected to an NOx elimination test under the following conditions.

[0039] 6 cc of the honeycomb catalyst was set into a quartz glass reactor tube. The reactor tube was inserted into an electric furnace and heat controlled so that the gas introduced into the reactor tube could be set to temperatures of 300° C., 400° C. and 500° C. The following gases were introduced into the reactor tube: a model gas, i.e. an assumed exhaust gas as would be emitted from an automobile engine operated in the theoretical air/fuel ratio (which will be hereinafter referred to as “stoichiometric model gas”) and a model gas, i.e. an assumed exhaust gas as would be emitted from a lean-burn operated automobile engine (which will be hereinafter referred to as “lean model gas”), where these two model gases were introduced into the reactor tube upon switching from one to another at every 3 minutes. The stoichiometric model gas had such a composition as NOx: 1,000 ppm, C₃H₆: 600 ppm, CO: 0.6%, CO₂: 12%, O₂: 0.5%, H₂: 0.3%, H₂O: 10%, and N₂: the balance. The lean model gas had such a composition as NOx: 600 ppm, C₃H₆: 500 ppm, CO: 0.1%, CO₂: 10%, O_(2: 5)%, H₂O: 10% and N₂: the balance. NOx concentration was measured at the inlet to and the outlet from the catalyst, and NOx elimination efficiency one minute after switching to the lean model gas was calculated according to the following equation:

NOx elimination efficiency (%)=(NOx concentration of inlet gas−NOx concentration of outlet gas)÷NOx concentration of inlet gas×100

[0040] Test for determining the NOx elimination efficiency as mentioned above will be referred to as Test Example 1.

[0041] (Test Results)

[0042] Test results of Example Catalysts 1 to 41 and Comparative Catalysts 1 to 14 according to Test Example 1 are shown in Table 1. In the fuel-rich burn operation, all the catalysts constantly had an NOx elimination efficiency of 90% or more at 300° C. and 100% at 400° C., showing the satisfactory ternary catalyst activity. In case of the present catalysts, the NOx elimination efficiency was not changed during both of the lean-burn operation and the stoichiometric burn operation even after a plurality of switched operations. The HC and CO elimination efficiency during the lean-burn operation was 90% or more. Example Catalyst containing at least one member of alkali metals and alkaline earth metals, and all of Mn and Rh, Pt and Pd had evidently higher NOx elimination efficiencies than those of Comparative Example Catalysts. TABLE 1 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example Catalyst 1 0.8NaMnPd—RhPt/Al2O3 88 92 87 Example Catalyst 2 0.8LiMnPd—RhPt/Al₂O₃ 86 88 71 Example Catalyst 3 0.8KMnPd—RhPt/Al₂O₃ 82 96 91 Example Catalyst 4 0.8RbMnPd—RhPt/Al₂O₃ 87 97 94 Example Catalyst 5 0.8CsMnPd—RhPt/Al₂O₃ 83 99 95 Example Catalyst 6 0.8MgMnPd—RhPt/Al₂O₃ 71 85 63 Example Catalyst 7 0.8CaMnPd—RhPt/Al₂O₃ 82 93 75 Example Catalyst 8 0.8SrMnPd—RhPt/Al₂O₃ 82 92 80 Example Catalyst 9 0.8BaMnPd—RhPt/Al₂O₃ 73 71 54 Example Catalyst 10 0.2Li0.6NaMnPd—RhPt/Al₂O₃ 82 91 73 Example Catalyst 11 0.4Li0.4KMnPd—RhPt/Al₂O₃ 85 94 92 Example Catalyst 12 0.4Li0.4RbMnPd—RhPt/Al₂O₃ 75 77 69 Example Catalyst 13 0.4Li0.4CsMnPd—RhPt/Al₂O₃ 85 93 91 Example Catalyst 14 0.6Li0.1MgMnPd—RhPt/Al₂O₃ 72 61 50 Example Catalyst 15 0.4Li0.4CaMnPd—RhPt/Al₂O₃ 75 91 77 Example Catalyst 16 0.4Li0.4SrMnPd—RhPt/Al₂O₃ 84 90 75 Example Catalyst 17 0.4Li0.4BaMnPd—RhPt/Al₂O₃ 72 70 55 Example Catalyst 18 0.8Na0.6KMnPd—RhPt/Al₂O₃ 91 90 93 Example Catalyst 19 0.8Na0.4RbMnPd—RhPt/Al₂O₃ 85 80 81 Example Catalyst 20 0.8Na0.4CsMnPd—RhPt/Al₂O₃ 86 90 85 Example Catalyst 21 0.8Na0.75MgMnPd—RhPt/Al₂O₃ 92 99 94 Example Catalyst 22 0.8Na0.4CaMnPd—RhPt/Al₂O₃ 80 90 71 Example Catalyst 23 0.4Na0.2SrMnPd—RhPt/Al₂O₃ 89 87 81 Example Catalyst 24 0.4K0.2CsMnPd—RhPt/Al₂O₃ 95 98 85 Example Catalyst 25 0.4K0.4RbMnPd—RhPt/Al₂O₃ 81 85 73 Example Catalyst 26 0.4K0.4CaMnPd—RhPt/Al₂O₃ 80 80 63 Example Catalyst 27 0.6K0.4SrMnPd—RhPt/Al₂O₃ 82 86 75 Example Catalyst 28 0.6K0.4BaMnPd—RhPt/Al₂O₃ 80 76 77 Example Catalyst 29 0.3Cs0.1MgMnPd—RhPt/Al₂O₃ 85 90 85 Example Catalyst 30 0.3Cs0.2CaMnPd—RhPt/Al₂O₃ 82 85 80 Example Catalyst 31 0.3Cs0.4SrMnPd—RhPt/Al₂O₃ 86 88 75 Example Catalyst 32 0.3Cs0.4BaMnPd—RhPt/Al₂O₃ 73 85 80 Example Catalyst 33 0.4Sr0.1MgMnPd—RhPt/Al₂O₃ 88 90 82 Example Catalyst 34 0.4Sr0.4CaMnPd—RhPt/Al₂O₃ 81 85 78 Example Catalyst 35 0.4Sr0.4BaMnPd—RhPt/Al₂O₃ 71 82 77 Example Catalyst 36 0.4Li1.2Na0.6KMnPd—RhPt/Al₂O₃ 98 99 91 Example Catalyst 37 0.8Na0.2Ca0.1MgMnPd—RhPt/Al₂O₃ 80 87 75 Example Catalyst 38 0.4Na0.15Sr0.1MgMnPd—RhPt/Al₂O₃ 83 88 78 Example Catalyst 39 0.4Na0.15Sr0.2CaMnPd—RhPt/Al₂O₃ 76 80 70 Example Catalyst 40 0.4Li0.4K0.2SrMnPd—RhPt/Al₂O₃ 88 93 90 Example Catalyst 41 0.4Li0.4Na0.4K0.2CsMnPd—RhPt/Al₂O₃ 95 98 95 Comp. Ex. Catalyst 1 0.8NaPd—RhPt/Al₂O₃ 67 63 35 Comp. Ex. Catalyst 2 0.8LiPd—RhPt/Al₂O₃ 68 51 35 Comp. Ex. Catalyst 3 0.8KPd—RhPt/Al₂O₃ 58 57 42 Comp. Ex. Catalyst 4 0.8RbPd—RhPt/Al₂O₃ 40 59 47 Comp. Ex. Catalyst 5 0.8CsPd—RhPt/Al₂O₃ 35 61 50 Comp. Ex. Catalyst 6 0.8MgPd—RhPt/Al₂O₃ 50 38 23 Comp. Ex. Catalyst 7 0.8CaPd—RhPt/Al₂O₃ 58 52 28 Comp. Ex. Catalyst 8 0.8SrPd—RhPt/Al₂O₃ 51 57 36 Comp. Ex. Catalyst 9 0.8BaPd—RhPt/Al₂O₃ 57 51 32 Comp. Ex. Catalyst 10 0.8Na0.1MgPd—RhPt/Al₂O₃ 52 60 40 Comp. Ex. Catalyst 11 0.4Sr0.4BaPd—RhPt/Al₂O₃ 49 61 29 Comp. Ex. Catalyst 12 0.6K0.4BaPd—RhPt/Al₂O₃ 55 53 30 Comp. Ex. Catalyst 13 0.8Na0.2Ca0.1MgPd—RhPt/Al₂O₃ 51 55 40 Comp. Ex. Catalyst 14 0.4Na0.15Sr0.2CaPd—RhPt/Al₂O₃ 54 49 36

TEST EXAMPLE 2

[0043] (Test Procedure)

[0044] Example Catalyst 1, 3, 8, 11, 18, 21, 33, 36, 38 and 40, and Comparative Example Catalyst 1 to 5, 11 and 13 were fired at 800° C. for 5 hours, and then subjected to the test in the same test procedure as Test Example 1.

[0045] (Test Results)

[0046] Test results are shown in Table 2. The present catalysts had evidently higher NOx elimination efficiencies than those of Comparative Example Catalysts and had distinguished high temperature durabilities. TABLE 2 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example Catalyst 1 0.8NaMnPd—RhPt/Al₂O₃ 73 85 73 Example Catalyst 3 0.8KMnPd—RhPt/Al₂O₃ 75 80 70 Example Catalyst 8 0.8SrMnPd—RhPt/Al₂O₃ 78 80 69 Example Catalyst 11 0.4Li0.4KMnPd—RhPt/Al₂O₃ 80 85 84 Example Catalyst 18 0.8Na0.6KMnPd—RhPt/Al₂O₃ 79 82 87 Example Catalyst 21 0.8Na0.075MgMnPd—RhPt/Al₂O₃ 88 91 89 Example Catalyst 33 0.4Sr0.1MgMnPd—RhPt/Al₂O₃ 72 79 69 Example Catalyst 36 0.4Li1.2Na0.6KMnPd—RhPt/Al₂O₃ 83 93 88 Example Catalyst 38 0.4Na0.15Sr0.1MgMnPd—RhPt/Al₂O₃ 75 81 72 Example Catalyst 40 0.4Li0.4K0.2SrMnPd—RhPt/Al₂O₃ 80 76 69 Comp. Ex. Catalyst 1 0.8NaPd—RhPt/Al₂O₃ 41 40 15 Comp. Ex. Catalyst 2 0.8LiPd—RhPt/Al₂O₃ 35 39 21 Comp. Ex. Catalyst 3 0.8KPd—RhPt/Al₂O₃ 45 48 35 Comp. Ex. Catalyst 4 0.8RbPd—RhPt/Al₂O₃ 33 49 34 Comp. Ex. Catalyst 5 0.8CsPd—RhPt/Al₂O₃ 35 33 21 Comp. Ex. Catalyst 11 0.4Sr0.4BaPd—RhPt/Al₂O₃ 24 40 22 Comp. Ex. Catalyst 13 0.8Na0.2Ca0.1MgPd—RhPt/Al₂O₃ 38 40 31

EXAMPLE 2

[0047] In the same manner as in Example 1, Example Catalysts 42 to 47 were prepared by adding Cu, Co or Ni to Example Catalysts 21 and 36, respectively, and evaluated according to Test Example 1. Amounts of supported Cu, Co and Ni were 0.1 part by mole each in terms of metal elements on the basis of 1.5 parts by mole of alumina.

[0048] (Test Results)

[0049] Test results are shown in Table 3. Example Catalysts containing Co, Ni or Cu had higher activities than those of Comparative Example Catalysts 1 to 14 shown in Table 1. TABLE 3 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example Catalyst 42 NaMgMnPd—RhPt0.1Cu/Al₂O₃ 93 99 96 Example Catalyst 43 NaMgMnPd—RhPt0.1Co/Al₂O₃ 94 99 95 Example Catalyst 44 NaMgMnPd—RhPt0.1Ni/Al₂O₃ 95 99 97 Example Catalyst 45 LiNaKMnPd—RhPt0.1Cu/Al₂O₃ 87 95 93 Example Catalyst 46 LiNaKMnPd—RhPt0.1Co/Al₂O₃ 86 96 94 Example Catalyst 47 LiNaKMnPd—RhPt0.1Ni/Al₂O₃ 84 99 93

EXAMPLE 3

[0050] In the same manner as in Example 1, Example Catalysts 48 to 51 were prepared by adding Ti or Si to Example Catalysts 21 and 36, respectively. Amounts of supported Ti and Si were 0.1 parts by mole each in terms of metal elements on the basis of 1.5 parts by mole of alumina.

TEST EXAMPLE 3

[0051] (Test Procedure)

[0052] In Test Example 1, only an SO₂-added lean gas was passed through the reaction tube. An amount of SO₂ added to the lean gas was 0.01%. Then, an NOx elimination efficiency was determined according to the procedure of Test Example 1. Test temperature was 400° C.

[0053] (Test Results)

[0054] Test results of Example Catalysts 48 to 51 and Comparative Example Catalysts 1 and 3 according to Test Example 3 are shown in Table 4. Example Catalysts 48 to 51 had higher NOx elimination efficiencies than those of Comparative Example Catalysts 1 and 3 and also had a good SOx durability. TABLE 4 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example NaMgMnPd0.1Ti—RhPt/Al₂O₃ 61 68 58 Catalyst 48 Example NaMgMnPd0.1Si—RhPt/Al₂O₃ 59 62 55 Catalyst 49 Example LiNaKMnPd0.1Ti—RhPt/Al₂O₃ 70 75 71 Catalyst 50 Example LiNaKMnPd0.1Si—RhPt/Al₂O₃ 65 70 58 Catalyst 51 Comp. Ex. 0.8NaPd—RhPt/Al₂O₃ 28 32 15 Catalyst 1 Comp. Ex. 0.8KPd—RhPt/Al₂O₃ 20 24 32 Catalyst 3

EXAMPLE 4

[0055] In the same manner as in Example 1, Example Catalysts 52 to 60 were prepared by adding 0.2 parts by mole of Ce, La or Nd in terms of metal elements to Example Catalysts 36, 48 and 50, respectively, on the basis of 1.5 parts by mole of alumina. Test was the same as in Test Example 2.

[0056] (Test Results)

[0057] NOx elimination efficiencies determined according to Test Example 2 are shown in Table 5. Example Catalysts 52 to 60 had evidently higher NOx elimination efficiencies than those of Comparative Example Catalysts shown in Table 2 and had good high temperature durabilities. TABLE 5 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example Catalyst 52 LiNaKMnPd—RhPt—0.2Ce/Al₂O₃ 88 95 91 Example Catalyst 53 LiNaKMnPd—RhPt—0.2La/Al₂O₃ 83 96 89 Example Catalyst 54 LiNaKMnPd—RhPt—0.2Nd/Al₂O₃ 85 93 90 Example Catalyst 55 NaMgMnPdTi—RhPt—0.2Ce/Al₂O₃ 93 95 85 Example Catalyst 56 NaMgMnPdTi—RhPt—0.2La/Al₂O₃ 88 92 87 Example Catalyst 57 NaMgMnPdTi—RhPt—0.2Nd/Al₂O₃ 90 91 91 Example Catalyst 58 LiNaKMnPdTi—RhPt—0.2Ce/Al₂O₃ 95 97 94 Example Catalyst 59 LiNaKMnPdTi—RhPt—0.2La/Al₂O₃ 82 91 91 Example Catalyst 60 LiNaKMnPdTi—RhPt—0.2Nd/Al₂O₃ 80 91 80

EXAMPLE 5

[0058] In the same manner as in Example 1, Example Catalysts 61 to 66 were prepared by omitting one of the noble metals from Example Catalysts 52 and 58. Test was the same as in Test Example 2.

[0059] (Test Results)

[0060] NOx elimination efficiencies determined according to Test Example 2 are shown in Table 6. Example Catalysts 61 to 66 had evidently higher NOx elimination efficiencies than those of Comparative Example catalysts shown in Table 2 and had good high temperature durabilities. TABLE 6 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example LiNaKMnPd—Pt—Ce/Al₂O₃ 79 86 73 Catalyst 61 Example LiNaKMnPd—RhCe/Al₂O₃ 73 86 77 Catalyst 62 Example LiNaKMn—RhPt—Ce/Al₂O₃ 70 86 80 Catalyst 63 Example LiNaKMnPdTi—Pt—Ce/Al₂O₃ 86 90 78 Catalyst 64 Example LiNaKMnPdTi—Rh—Ce/Al₂O₃ 89 90 80 Catalyst 65 Example LiNaKMnTi—RhPt—Ce/Al₂O₃ 79 91 83 Catalyst 66

EXAMPLE 6

[0061] In the same manner as in Example 1, Example Catalysts 67 to 72 were prepared by adding 0.1 part by mole of at least one of P and B in terms of elements to Example Catalysts 52 and 58, respectively, on the basis of 1.5 parts by mole of alumina. Test was the same as in Test Example 2.

[0062] (Test Results)

[0063] NOx elimination efficiencies determined according to Test Example 2 are shown in Table 7. Example Catalysts 67 to 72 had higher NOx elimination efficiencies than those of Comparative Example Catalysts shown in Table 2 and had good high temperature durabilities. TABLE 7 NOx elimination efficiency (%) Catalyst 300° C. 400° C. 500° C. Example Catalyst 67 LiNaKMnPd0.1P—RhPt—Ce/Al₂O₃ 88 87 94 Example Catalyst 68 LiNaKMnPd0.1B—RhPt—Ce/Al₂O₃ 83 82 95 Example Catalyst 69 LiNaKMnPd0.1P0.1B—RhPt—Ce/Al₂O₃ 85 81 92 Example Catalyst 70 LiNaKMnPdTi0.1P—RhPt—Ce/Al₂O₃ 81 93 92 Example Catalyst 71 LiNaKMnPdTi0.1B—RhPt—Ce/Al₂O₃ 80 83 87 Example Catalyst 72 LiNaKMnPdTi0.1P0.1B—RhPt—Ce/Al₂O₃ 80 86 97

EXAMPLE 7

[0064] In the same manner as in Example 1, Catalysts containing 0.1 part by mole of Ti in terms of metal element on the basis of 1.5 parts by mole of alumina were prepared by adding Ti to Example Catalysts 11 and 33 and catalysts were also prepared by changing Mn contents of Example Catalysts 36 and 48. Test was the same as in Test Example 1.

[0065] (Test Results)

[0066] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 8. The catalysts containing 0.05 to 2 parts by mole of supported Mn in terms of metal element had high NOx elimination efficiencies than 80%, showing good NOx elimination efficiencies. TABLE 8 NOx elimination NOx elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. LiKPdTi—RhPt/Al₂O₃ 73 LiNaKPd—RhPt/Al₂O₃ 70 LiK0.02MnPdTi—RhPt/Al₂O₃ 75 LiNaK0.2MnPd—RhPt/Al₂O₃ 75 LiK0.05MnPdTi—RhPt/Al₂O₃ 83 LiNaK0.05MnPd—RhPt/Al₂O₃ 82 LiK0.2MnPdTi—RhPt/Al₂O₃ 92 LiNaK0.2MnPd—RhPt/Al₂O₃ 99 LiK0.4MnPdTi—RhPt/Al₂O₃ 98 LiNaK0.4MnPd—RhPt/Al₂O₃ 99 LiK1.4MnPdTi—RhPt/Al₂O₃ 90 LiNaK1.4MnPdRhPt/Al₂O₃ 93 LiK2MnPdTi—RhPt/Al₂O₃ 82 LiNaK2MnPd—RhPt/Al₂O₃ 86 LiK3MnPdTi—RhPt/Al₂O₃ 68 LiNaK3MnPd—RhPt/Al₂O₃ 71 SrMgPdTi—RhPt/Al₂O₃ 69 NaMgPdTi—RhPt/Al₂O₃ 71 SrMg0.02MnPdTi—RhPt/Al₂O₃ 75 NaMg0.02MnPdTi—RhPt/Al₂O₃ 73 SrMg0.05MnPdTi—RhPt/Al₂O₃ 81 NaMg0.05MnPdTi—RhPt/Al₂O₃ 81 SrMg0.2MnPdTi—RhPt/Al₂O₃ 85 NaMg0.2MnPdTi—RhPt/Al₂O₃ 96 SrMg0.4MnPdTi—RhPt/Al₂O₃ 93 NaMg0.4MnPdTi—RhPt/Al₂O₃ 93 SrMg1.4MnPdTi—RhPt/Al₂O₃ 88 NaMg1.4MnPdTi—RhPt/Al₂O₃ 88 SrMg2MnPdTi—RhPt/Al₂O₃ 83 NaMg2MnPdTi—RhPt/Al₂O₃ 83 SrMg3MnPdTi—RhPt/Al₂O₃ 62 NaMg3MnPdTi—RhPt/Al₂O₃ 65

EXAMPLE 8

[0067] In the same manner as in Example 1, catalysts containing 0.1 part by mole of Ti in terms of metal element on the basis of 1.5 parts by mole of alumina were prepared by adding Ti to Example Catalysts 11 and 33, and catalysts whose K and Sr contents were further changed in the prepared catalysts and catalysts whose K and Na contents were changed in Example Catalysts 36 and 48 were also prepared. Test was the same as in Test Example 1.

[0068] (Test Results)

[0069] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 9. The catalysts having K, Sr and Na contents of 0.05 to 3 parts by mole each had higher NOx elimination efficiencies than 80% at 400° C., showing good NOx elimination efficiencies. TABLE 9 NOx elimination NOx elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. Li0.02KMnPdTi—RhPt/Al₂O₃ 72 LiNa0.02KMnPd—RhPt/Al₂O₃ 70 Li0.05KMnPdTi—RhPt/Al₂O₃ 81 LiNa0.05KMnPd—RhPt/Al₂O₃ 84 Li0.4KMnPdTi—RhPt/Al₂O₃ 92 LiNa0.4KMnPd—RhPt/Al₂O₃ 99 Li1.5KMnPdTi—RhPt/Al₂O₃ 96 LiNa0.6KMnPd—RhPt/Al₂O₃ 99 Li2.2KMnPdTi—RhPt/Al₂O₃ 89 LiNa1.5KMnPd—RhPt/Al₂O₃ 90 Li3KMnPdTi—RhPt/Al₂O₃ 83 LiNa3KMnPd—RhPt/Al₂O₃ 82 Li4KMnPdTi—RhPt/Al₂O₃ 69 LiNa4KMnPd—RhPt/Al₂O₃ 73 0.02SrMgMnPdTi—RhPt/Al₂O₃ 73 0.02NaMgMnPdTi—RhPt/Al₂O₃ 62 0.05SrMgMnPdTi—RhPt/Al₂O₃ 81 0.05NaMgMnPdTi—RhPt/Al₂O₃ 81 0.4SrMgMnPdTi—RhPt/Al₂O₃ 85 0.5NaMgMnPdTi—RhPt/Al₂O₃ 88 0.6SrMgMnPdTi—RhPt/Al₂O₃ 88 0.8NaMgMnPdTi—RhPt/Al₂O₃ 96 1.5SrMgMnPdTi—RhPt/Al₂O₃ 83 2NaMgMnPdTi—RhPt/Al₂O₃ 90 3SrMgMnPdTi—RhPt/Al₂O₃ 81 3NaMgMnPdTi—RhPt/Al₂O₃ 84 4SrMgMnPdTi—RhPt/Al₂O₃ 62 4NaMgMnPdTi—RhPt/Al₂O₃ 76

EXAMPLE 9

[0070] In the same manner as in Example 1, catalysts whose Rh, Pt and Pd contents were changed in Example Catalyst 48 were prepared. Test was the same as in Test Example 1.

[0071] (Test Results)

[0072] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 10. The catalysts containing 0.002 to 0.05 parts by mole of Pt, 0.0003 to 0.01 part by mole of Rh and 0.001 to 0.2 parts by mole of Pd in terms of metal elements as amounts of supported Rh, Pt and Pd had higher NOx elimination efficiencies than 80% at 400° C., showing good NOx elimination efficiencies. TABLE 10 NOx elimination NOx elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. NaMgMn0.001PdTi—0.0003Rh0.001Pt/Al₂O₃ 60 NaMgMn0.014PdTi—0.0003Rh0.001Pt/Al₂O₃ 76 NaMgMn0.0001PdTi—0.01Rh0.001Pt/Al₂O₃ 68 NaMgMn0.014PdTi—0.01Rh0.001Pt/Al₂O₃ 74 NaMgMn0.001PdTi—0.0001Rh0.002Pt/Al₂O₃ 62 NaMgMn0.014PdTi—0.0001Rh0.002Pt/Al₂O₃ 73 NaMgMn0.001PdTi—0.0003Rh0.002Pt/Al₂O₃ 84 NaMgMn0.014PdTi—0.0003Rh0.002Pt/Al₂O₃ 83 NaMgMn0.001Pdti—0.0022Rh0.002Pt/Al₂O₃ 90 NaMgMn0.014PdTi—0.0022Rh0.002Pt/Al₂O₃ 92 NaMgMn0.001PdTi—0.01Rh0.002Pt/Al₂O₃ 81 NaMgMn0.014PdTi—0.01Rh0.002Pt/Al₂O₃ 84 NaMgMn0.001PdTi—0.02Rh0.002Pt/Al₂O₃ 73 NaMgMn0.014PdTi—0.02Rh0.002Pt/Al₂O₃ 76 NaMgMn0.001PdTi—0.0003Rh0.014Pt/Al₂O₃ 85 NaMgMn0.014PdTi—0.0003Rh0.014Pt/Al₂O₃ 86 NaMgMn0.001PdTi—0.0022Rh0.014Pt/Al₂O₃ 95 NaMgMn0.014PdTi—0.0022Rh0.014Pt/Al₂O₃ 96 NaMgMn0.001PdTi—0.01Rh0.014Pt/Al₂O₃ 84 NaMgMn0.014PdTi—0.01Rh0.014Pt/Al₂O₃ 87 NaMgMn0.001PdTi—0.0001Rh0.05Pt/Al₂O₃ 75 NaMgMn0.014PdTi—0.0001Rh0.05Pt/Al₂O₃ 75 NaMgMn0.001PdTi—0.0003Rh0.05Pt/Al₂O₃ 81 NaMgMn0.014PdTi—0.0003Rh0.05Pt/Al₂O₃ 82 NaMgMn0.001PdTi—0.0022Rh0.05Pt/Al₂O₃ 88 NaMgMn0.014PdTi—0.0022Rh0.05Pt/Al₂O₃ 95 NaMgMn0.001PdTi—0.01Rh0.05Pt/Al₂O₃ 84 NaMgMn0.014PdTi—0.01Rh0.05Pt/Al₂O₃ 88 NaMgMn0.001PdTi—0.02Rh0.05Pt/Al₂O₃ 75 NaMgMn0.014PdTi—0.02Rh0.05Pt/Al₂O₃ 75 NaMgMn0.001PdTi—0.0003Rh0.07Pt/Al₂O₃ 72 NaMgMn0.014PdTi—0.0003Rh0.07Pt/Al₂O₃ 73 NaMgMn0.001PdTi—0.01Rh0.07Pt/Al₂O₃ 73 NaMgMn0.014PdTi—0.01Rh0.07Pt/Al₂O₃ 71 NaMgMn0.2PdTi—0.0003Rh0.001Pt/Al₂O₃ 63 NaMgMn0.2PdTi—0.0001Rh0.05Pt/Al₂O₃ 74 NaMgMn0.2PdTi—0.01Rh0.001Pt/Al₂O₃ 66 NaMgMn0.2PdTi—0.0003Rh0.05Pt/Al₂O₃ 82 NaMgMn0.2PdTi—0.0001Rh0.002Pt/Al₂O₃ 68 NaMgMn0.2PdTi—0.0022Rh0.05Pt/Al₂O₃ 88 NaMgMn0.2PdTi—0.0003Rh0.002Pt/Al₂O₃ 81 NaMgMn0.2PdTi—0.01Rh0.05Pt/Al₂O₃ 81 NaMgMn0.2PdTi—0.0022Rh0.002Pt/Al₂O₃ 90 NaMgMn0.2PdTi—0.02Rh0.05Pt/Al₂O₃ 77 NaMgMn0.2PdTi—0.01Rh0.002Pt/Al₂O₃ 83 NaMgMn0.2PdTi—0.0003Rh0.07Pt/Al₂O₃ 76 NaMgMn0.2PdTi—0.02Rh0.002Pt/Al₂O₃ 71 NaMgMn0.2PdTi—0.01Rh0.07Pt/Al₂O₃ 78 NaMgMn0.2PdTi—0.0003Rh0.014Pt/Al₂O₃ 84 NaMgMn0.0005PdTi—0.0022Rh0.014Pt/Al₂O₃ 70 NaMgMn0.2PdTi—0.0022Rh0.014Pt/Al₂O₃ 93 NaMgMn0.3PdTi—0.0022Rh0.014Pt/Al₂O₃ 71 NaMgMn0.2PdTi—0.01Rh0.014Pt/Al₂O₃ 87

EXAMPLE 10

[0073] In the same manner as in Example 1, catalysts were prepared by adding Ce, La or Nd to Example Catalysts 36 and 48 and by further changing their contents. Test was the same as in Test Example 2.

[0074] (Test Results)

[0075] NOx elimination efficiencies determined at 400° C. according to Test Example 2 are shown in Table 11. The catalysts containing 0.02 to 0.5 parts by mole of supported Ce, La and Nd in terms of metal elements had higher NOx elimination efficiencies than 80% at 400° C. after heating at 800° C. for 5 hours, showing good NOx elimination efficiencies. TABLE 11 NOx NOx elimination elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. LiNaKMnPd-RhPt- 75 NaMgMnPdTi-RhPt- 76 0.01Ce/Al₂O₃ 0.01Ce/Al₂O₃ LiNaKMnPd-RhPt- 82 NaMgMnPdTi-RhPt- 87 0.02Ce/Al₂O₃ 0.02Ce/Al₂O₃ LiNaKMnPd-RhPt- 95 NaMgMnPdTi-RhPt- 95 0.2Ce/Al₂O₃ 0.2Ce/Al₂O₃ LiNaKMnPd-RhPt- 91 NaMgMnPdTi-RhPt- 94 0.5Ce/Al₂O₃ 0.5Ce/Al₂O₃ LiNaKMnPd-RhPt- 73 NaMgMnPdTi-RhPt- 71 0.8Ce/Al₂O₃ 0.8Ce/Al₂O₃ LiNaKMnPd-RhPt- 75 NaMgMnPdTi-RhPt- 76 0.01La/Al₂O₃ 0.01La/Al₂O₃ LiNaKMnPd-RhPt- 85 NaMgMnPdTi-RhPt- 85 0.02La/Al₂O₃ 0.02La/Al₂O₃ LiNaKMnPd-RhPt- 96 NaMgMnPdTi-RhPt- 92 0.2La/Al₂O₃ 0.2La/Al₂O₃ LiNaKMnPd-RhPt- 88 NaMgMnPdTi-RhPt- 82 0.5La/Al₂O₃ 0.5La/Al₂O₃ LiNaKMnPd-RhPt- 74 NaMgMnPdTi-RhPt- 63 0.8La/Al₂O₃ 0.8La/Al₂O₃ LiNaKMnPd-RhPt- 66 NaMgMnPdTi-RhPt- 70 0.01Nd/Al₂O₃ 0.01Nd/Al₂O₃ LiNaKMnPd-RhPt- 81 NaMgMnPdTi-RhPt- 82 0.02Nd/Al₂O₃ 0.2Nd/Al₂O₃ LiNaKMnPd-RhPt- 93 NaMgMnPdTi-RhPt- 91 0.2Nd/Al₂O₃ 0.2Nd/Al₂O₃ LiNaKMnPd-RhPt- 84 NaMgMnPdTi-RhPt- 84 0.5Nd/Al₂O₃ 0.5Nd/Al₂O₃ LiNaKMnPd-RhPt- 69 NaMgMnPdti-RhPt- 75 0.8Nd/Al₂O₃ 0.8Nd/Al₂O₃

EXAMPLE 11

[0076] In the same manner as in Example 1, catalysts were prepared by adding Cu, Co or Ni to Example Catalysts 36 and 48 and by further changing their contents.

[0077] (Test Results)

[0078] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 12. The catalysts containing 0.01 to 2 parts by mole of Cu, Co or Ni in terms of metal elements had higher NOx elimination efficiencies than 80% at 400° C., showing good NOx elimination efficiencies. TABLE 12 NOx NOx elimination elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. LiNaKMnPd-RhPt- 75 NaMgMnPdTi-RhPt- 76 0.005Cu/Al₂O₃ 0.005Cu/Al₂O₃ LiNaKMnPd-RhPt- 85 NaMgMnPdTi-RhPt- 82 0.01Cu/Al₂O₃ 0.01Cu/Al₂O₃ LiNaKMnPd-RhPt- 92 NaMgMnPdTi-RhPt- 87 0.1Cu/Al₂O₃ 0.1Cu/Al₂O₃ LiNaKMnPd-RhPt- 96 NaMgMnPdTi-RhPt- 91 0.2Cu/Al₂O₃ 0.2Cu/Al₂O₃ LiNaKMnPd-RhPt- 81 NaMgMnPdTi-RhPt- 83 2Cu/Al₂O₃ 2Cu/Al₂O₃ LiNaKMnPd-RhPt- 70 NaMgMnPdTi-RhPt- 74 3Cu/Al₂O₃ 3Cu/Al₂O₃ LiNaKMnPd-RhPt- 71 NaMgMnPdTi-RhPt- 71 0.005Co/Al₂O₃ 0.005Co/Al₂O₃ LiNaKMnPd-RhPt- 81 NaMgMnPdTi-RhPt- 88 0.01Co/Al₂O₃ 0.01Co/Al₂O₃ LiNaKMnPd-RhPt- 94 NaMgMnPdTi-RhPt- 94 0.1Co/Al₂O₃ 0.1Co/Al₂O₃ LiNaKMnPd-RhPt- 97 NaMgMnPdTi-RhPt- 98 0.2Co/Al₂O₃ 0.2Co/Al₂O₃ LiNaKMnPd-RhPt- 81 NaMgMnPdTi-RhPt- 83 2Co/Al₂O₃ 2Co/Al₂O₃ LiNaKMnPd-RhPt- 77 NaMgMnPdTi-RhPt- 71 3Co/Al₂O₃ 3Co/Al₂O₃ LiNaKMnPd-RhPt- 71 NaMgMnPdTi-RhPt- 74 0.005Ni/Al₂O₃ 0.005Ni/Al₂O₃ LiNaKMnPd-RhPt- 83 NaMgMnPdTi-RhPt- 81 0.01Ni/Al₂O₃ 0.01Ni/Al₂O₃ LiNaKMnPd-RhPt- 84 NaMgMnPdTi-RhPt- 82 0.1Ni/Al₂O₃ 0.1Ni/Al₂O₃ LiNaKMnPd-RhPt- 86 NaMgMnPdTi-RhPt- 83 0.2Ni/Al₂O₃ 0.2Ni/Al₂O₃ LiNaKMnPd-RhPt- 83 NaMgMnPdTi-RhPt- 83 2Ni/Al₂O₃ 2Ni/Al₂O₃ LiNaKMnPd-RhPt- 76 NaMgMnPdTi-RhPt- 76 3Ni/Al₂O₃ 3Ni/Al₂O₃

EXAMPLE 12

[0079] In the same manner as in Example 1, catalysts were prepared by adding Ti or Si to Example Catalyst 36 while changing its contents, and also by changing Ti content of Example Catalyst 48 or by adding Si to Example Catalyst 48 while changing its content.

[0080] (Test Results)

[0081] NOx elimination efficiencies determined at 400° C. according to Test Example 3 are shown in Table 13. The catalysts containing 0.01 to 2 parts by mole of supported Ti or Si in terms of metal elements had a higher NOx elimination efficiency than 50% at 400C after SOx poisoning, showing high NOx elimination efficiencies. TABLE 13 NOx NOx elimi- elimi- nation nation efficiency efficiency (%), (%), Catalysts 400° C. Catalysts 400° C. LiNaKMnPd-0.005Ti- 39 NaMgMnPd0.005Ti- 43 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.01Ti- 54 NaMgMnPd0.01Ti- 57 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.1Ti- 75 NaMgMnPd0.1Ti- 68 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.2Ti- 79 NaMgMnPd0.2Ti- 76 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd2Ti- 58 NaMgMnPd2Ti- 51 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd3Ti- 43 NaMgMnPd3Ti- 34 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.005Si- 46 NaMgMnPd0.005Si- 41 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.01Si- 64 NaMgMnPd0.01Si- 54 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.1Si- 70 NaMgMnPd0.1Si- 62 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd0.2Si- 62 NaMgMnPd0.2Si- 60 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd2Si- 53 NaMgMnPd2Si- 56 RhPt/Al₂O₃ RhPt/Al₂O₃ LiNaKMnPd3Si- 39 NaMgMnPd3Si- 39 RhPt/Al₂O₃ RhPt/Al₂O₃

EXAMPLE 13

[0082] In the same manner as in Example 1, catalysts were prepared by changing P and B contents of Example Catalysts 70 and 71. Test was the same as in Test Example 2.

[0083] (Test Results)

[0084] NOx elimination efficiencies determined at 500° C. according to Test Example 2 are shown in Table 14. The catalyst containing 0.01 to 2 parts by mole of supported P or B in terms of elements on the basis of 1.5 parts by mole of alumina had higher NOx elimination efficiencies than 80% at 500° C. after heating at 800° C. for 5 hours, showing good NOx elimination efficiencies. TABLE 14 NOx NOx elimi- elimi- nation nation efficiency efficiency (%), (%), Catalysts 400° C. Catalysts 400° C. LiNaKMnPdTi0.01P- 95 LiNaKMnPdTi0.01B- 95 RhPt-Ce/Al₂O₃ RhPt-Ce/Al₂O₃ LiNaKMnPdTiP- 92 LiNaKMnPdTi1B- 88 RhPt-Ce/Al₂O₃ RhPt-Ce/Al₂O₃ LiNaKMnPdTi2P- 86 LiNaKMnPdTi2B- 81 RhPt-Ce/Al₂O₃ RhPt-Ce/Al₂O₃ LiNaKMnPdTi3P- 73 LiNaKMnPdTi3B- 71 RhPt-Ce/Al₂O₃ RhPt-Ce/Al₂O₃

EXAMPLE 14

[0085] In the same manner as in Example 1, catalysts were prepared by changing only amounts of coating per l of the honeycomb in Example Catalysts 36 and 48 without changing amounts of other supported components on A₂O₃.

[0086] (Test Results)

[0087] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 15. The catalysts containing 0.3 to 4 moles of A₂O₃ coating/l of honeycomb in terms of A₂O₃ had higher NOx elimination efficiencies than 80% at 400° C., showing good NOx elimination efficiencies. TABLE 15 NOx NOx elimination elimination efficiency efficiency Catalysts (%), 400° C. Catalysts (%), 400° C. LiNaKMnPd-RhPt/ 64 NaMgMnPdTi-RhPt/ 77 0.1Al₂O₃ 0.1Al₂O₃ LiNaKMnPd-RhPt/ 82 NaMgMnPdTi-RhPt/ 84 0.3Al₂O₃ 0.3Al₂O₃ LiNaKMnPd-RhPt/ 99 NaMgMnPdTi-RhPt/ 96 1.5Al₂O₃ 1.5Al₂O₃ LiNaKMnPd-RhPt/ 90 NaMgMnPdTi-RhPt/ 84 3Al₂O₃ 3Al₂O₃ LiNaKMnPd-RhPt/ 86 NaMgMnPdTi-RhPt/ 81 4Al₂O₃ 4Al₂O₃ LiNaKMnPd-RhPt/ 70 NaMgMnPdTi-RhPt/ 61 6Al₂O₃ 6Al₂O₃

EXAMPLE 15

[0088] As a hydrocarbon and CO combustion catalyst, a catalyst containing only Rh and Pt supported on an alumina coat honeycomb was prepared in the same manner as in Example 1, where Rh and Pt contents were 0.002 parts by mole of Rh and 0.01 part by mole of Pt in terms of metal elements on the basis of 1.5 parts by mole of alumina. Test was the same as in Test Example 1, and hydrocarbon and CO elimination efficiencies were determined by providing the combustion catalyst upstream or downstream of Example Catalyst 36 or 48 or with no provision of the combustion catalyst. Test temperature was 400° C.

[0089] (Test Results)

[0090] NOx elimination efficiencies determined at 400° C. according to Test Example 1 are shown in Table 16. Hydrocarbon and CO elimination efficiencies were improved by providing the combustion catalyst. TABLE 16 C₃H₆ elimination CO elimination efficiency (%), efficiency (%), 400° C. 400° C. Example Catalyst 36 Hydrocarbon and CO combustion 93 94 catalyst not provided Hydrocarbon and CO combustion 98 99 catalyst provided upstream Hydrocarbon and CO combustion 99 100 catalyst provided downstream Example Catalyst 48 Hydrocarbon and CO combustion 92 94 catalyst not provided Hydrocarbon and CO combustion 99 97 catalyst provided upstream Hydrocarbon and CO combustion 99 100 catalyst provided downstream

[0091] As described in detail above, nitrogen oxides can be eliminated with high efficiency in an oxygen excess atmosphere according to the present invention. The present catalyst has distinguished heat resistance and SOx resistance, so that a high elimination activity can be maintained for a long time.

INDUSTRIAL APPLICABILITY

[0092] Automobile exhaust gases are now on a trend toward global emission regulation and fuel economy regulation and it is expectable that the market for lean-burn automobiles will surely expand. For the automobile exhaust gas purification catalysts, ternary catalysts have been so far used, but have failed to eliminate NOx contained in the exhaust gases emitted from lean-burn automobiles. The present exhaust gas purification catalyst can eliminate NOx contained in the exhaust gases emitted from the lean-burn automobiles with high elimination efficiency and ensures a very high industrial applicability. 

1. An internal combustion engine exhaust gas purification apparatus, which comprises an exhaust gas purification catalyst provided in an internal combustion engine exhaust gas passage through which an air/fuel ratio-lean exhaust gas and an air/fuel ratio-rich or stoichiometric exhaust gas flows, characterized in that the exhaust gas purification catalyst comprises a porous carrier and an active component supported on the porous carrier, the active component comprising at least one member selected from Rh, Pt and Pd, at least one member selected from alkali metals and alkaline earth metals, and Mn.
 2. An internal combustion engine exhaust gas purification apparatus according to claim 1, characterized in that the active component further contains at least one of Ti and Si.
 3. An internal combustion engine exhaust gas purification apparatus according to claim 1, characterized in that the active component further contains at least one of Cu, Co and Ni.
 4. An internal combustion engine exhaust gas purification apparatus according to claim 1, characterized in that the active component further contains at least one of rare earth metals.
 5. An internal combustion engine exhaust gas purification apparatus according to claim 1, characterized in that the active component further contains at least one of P and B.
 6. An internal combustion engine exhaust gas purification apparatus according to claim 1, characterized in that a combustion catalyst capable of combusting HC and CO contained in the exhaust gas is provided at least at one of position upstream and downstream of the exhaust gas purification catalyst in the exhaust gas passage.
 7. An internal combustion engine exhaust gas purification process, which comprises contacting an exhaust gas emitted from a lean-burn operated internal combustion engine with an exhaust gas purification catalyst, thereby purifying the exhaust gas, characterized in that the exhaust gas is contacted with a catalyst comprising at least one member selected from Rh, Pt and Pd, at least one member selected from alkali metals and alkaline earth metals, and Mn, supported on a porous carrier.
 8. An internal combustion engine exhaust gas purification process according to claim 7, characterized in that operation of the internal combustion engine is temporarily shifted from the lean-burn operation to a theoretical air/fuel ratio operation or a fuel excess operation, thereby bringing an air/fuel ratio of the exhaust gas into a stoichiometric or fuel-rich state to regenerate the exhaust gas purification catalyst.
 9. An internal combustion engine exhaust gas purification process according to claim 7, characterized in that the exhaust gas is contacted with a combustion catalyst capable of combusting HC and CO and then with the exhaust gas purification catalyst.
 10. An internal combustion engine exhaust gas purification process according to claim 7, characterized in that the exhaust gas purified by the exhaust gas purification catalyst is further contacted with a combustion catalyst capable of combusting HC and CO.
 11. A lean NOx elimination catalyst, which comprises a porous carrier and an active component supported on the porous carrier, characterized in that the active component comprises at least one member selected from Rh, Pt and Pd, at least one member selected from alkali metals and alkaline earth metals, and Mn, amounts of supported active metals being 0.0003 to 0.01 part by mole of Rh, 0.002 to 0.05 parts by mole of Pt and 0.001 to 0.2 parts by mole of Pd, 0.05 to 3 parts by mole each of the alkali metals and alkaline earth metals and 0.05 to 2 parts by mole of Mn in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.
 12. A lean NOx elimination catalyst according to claim 11, characterized in that the active component contains all of Rh, Pt and Pd.
 13. A lean NOx elimination catalyst according to claim 11, characterized in that the active component further contains at least one of Ti and Si, amounts of supported Ti and Si being 0.01 to 2 parts by mole each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.
 14. A lean NOx elimination catalyst according to claim 11, characterized in that the active component further contains at least one of Ni, Co and Cu, amounts of supported Ni, Co and Cu being 0.01 to 2 parts by mole each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.
 15. A lean NOx elimination catalyst according to claim 11, characterized in that the active component further contains at least one of rare earth metals, amounts of supported rare earth metals being 0.02 to 0.5 parts by mole each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.
 16. A lean NOx elimination catalyst according to claim 11, characterized in that the active component further contains at least one of P and B, amounts of supported P and B being 0.01 to 2 parts by mole each in terms of metal elements on the basis of 1.5 parts by mole of the porous carrier.
 17. A lean NOx elimination catalyst according to claim 11, characterized in that the porous carrier is supported on a substrate, an amount of the supported porous carrier being 0.3 to 4 moles on the basis of 1 l of the subrate. 